DE1918066A1 - Polyurethane - Google Patents

Description

EGG. You Ρ0ΗΪ DE HBMOURS AHD COMPAHY 10th and Market Streets, Wilmington, Delaware 19 898, V.St.A.

Polyurethane

The invention relates to polyurethanes »They tertiary amino nitrogen atoms in the polymer chain entlialta &» and mixtures from such polyurethanes a with long-chain, synthetic, elastomeric polyurethanes; the invention also relates on moldings made from such semi-ohms »

Moldings based on long-chain, synthetic, elastomeric, coated polyurethanes ₉ special spandex fibers are known to suffer discoloration under the action of atmospheric conditions Polymer chain recurring »ureylenreate, ie contain residues of the formula -BH-CO-IH-. The tendency towards discoloration is more pronounced when the ureylene radical is bonded to a carbon atom of the aromatic ring.

From US Pat. No. 2,999,839 it is known that tertiary aliphatic · Aaine bit molecular weights above 280 segmented e Stabilize polyurethanes against discoloration. The in this-

909886/1807

ser patent specification beschrisoeaea amines? Ijeaonöesg the polymethacrylic acid esters., - soMtteen the polyurethanes against * Vsz * ~ staining under the binwlrlcuag of Lieasst and Hauah, glutinous but the breakdown of segssfitiarten polyurethanes at tor Chlorine bleach "British patent specification 1,104,127 describes an improvement over the USA »Patent 2 999 839» namely the use of more severely hindered methacrylic acid esters, which not only improves the dyeability of the polyurethanes and give protection against discoloration by light and smoke, but also to a reduced degradation upon exposure lead fluids containing chlorine. Still done also in this case® under certain washing conditions Use of chlorine-containing washing liquids is an essential® Impairment of the physical properties of the segmented Polyurethanes.

You new polyurethanes, the tertiary amino solvent atone -to the polymer! " tt · included and on other, '^ long-chain'. 'Synthetic, elastic, segmented® polyurethanes have a stabilizing effect, have recurring units of & llgßm® ± n0 &.

0 0
-E-HH-COR '»G-Ö-m«.

in which R and R * mean divalent aliphatiesh®, see or araliphatic Best® with molecular weight a imt @ ^ 400. At least one of the beds and E-R * © iitfeält ümm tertiary Aainostickstoffateia, the au to SWEi Kolalenat @ £ fat © s @ j üte neither a carboxyl group nor a eu eroioa-feigohsn include RISG, and bound to a tertiary butyl actual M © Polyurethanes according to the invention have logarittoisölie ¥ ise @@ S, -actual numbers from about 0.07 to 0.6, bestiamit, wi © aaeh "seeing".

The invention also relates to long-chain segoeaties © lastsmere Polyurethanes, which against the ultraYiolattss-See * ... po-

BATH ORIGINAL

v / ie Eaucfc mid MeoeX nrerureaciite §eli) £ ärteng st-mMlieiert, i ^ aesi sie one stafeilieiejröa & e KsagD © Ιϊιθβ Polyuretfesao der above bcsoferiebenen kind piiysilsaliBci-. 'asigeiaäsciit included. the end oil-loosening stabilized segsseB ^ iestea Polyiiretbsaea produced Porous bodies, wi® foils imcL Eaeera, - pin «bsatMMiges? against the Impairment of my physical properties, <I «h. the Pol ^ erisatabfcau, in sjhlorlialtigen bleaching liquids as Moldings made of polyurethanes, & ie in a previously known manner ainä stabilized with tertiary amines. In addition, the Sögmented Polsrurethane stabilized according to the invention good dyeability and IT color fastness.

The polyurethanes according to the invention are by. Reaction of a suitable monomer which contains a tertiary as-amino nitrogen atom bonded to a tert-butyl group (referred to below as U-tert-butyl group), prepared with suitable complementary monosing with additives suitable for the formation of poXytirethane. For example, a glycol containing a tert-butyl group is reacted with a diisooyanate, or a polyamide23. _r äae both - svrei l3E2 "soups as well as an IJ" -tert * Butfigru |>} / « & ιχύι £ ϊ. ^ _} w5" rd iDit a bis-chloroformic acid aster of a G-lycole izs! ges © tsgt "near Ilfflsstsuiigb" The first type produces a polyurethane "which contains the if-tert" butyl group in the R 'radical, while reactions of the last-mentioned type produce a polyurethane in which the N-tert-butyl group is in the R radical. The monomers can of course also be selected in such a way that each of the radicals R and R ^{1 contains} an H-tert-butyl group.

The binding sites of the radicals R and R ¹ are carbon atoms which neither belong to a carbonyl group nor to an aromatic ring & üri @ a. Otherwise, R and R 'can represent any desired divalent organic radicals. Si © should, however, not have any groups that could interfere with the condensation reaction leading to the formation of the polyurethane or give the product an undesirable color. The monomers should be

- 3 «,
9 0 98ÖS / 160 7

BATH

be chosen so that R and IV have molecular weights of less than 400. Aliphatic, cycloaliphatic and araliphatic radicals, which can also contain heteroatoms, such as O ₉ S ₉ Cl and Έ, are all suitable for Hoste H and R ** One of the two radicals R voaA B, ^f biusb, of course, a nitrogen £ - contain an atom in the form of an H-tert.-butyl group.

Following the preventive procedure for dividing the poly. urethane geniäse of the invention, a glycol containing the N-tert-butyl group is polymerized with a misocyanate. For this purpose, N-tert-butyl dialksnolamines, such as N-tert-butyl diethanolamine, are preferred. Such reactants form polyurethanes in which R * in the above general formula has the composition -Alk-Ii-Alk-, in which Alk has a never-

t-bu

whose alkylene radical with i bio 8 carbon atoms and t-Bu 6Λ, β_ tcrt.Butyl means «. S-TER1;> Bi "tyldiäthanol © sin is commercially available, but can be hergoptellt by tfcüsetaiüBg of tert.Eutylamin with Äthylenoxxd _β Higher homologs obtained by reaction of tort.But.yleimis SIIT üow eatsps © - ohenden Alkylenozid?. ? iud Bzt & plel kasn ^ -tart.Bttty tandiol-2,6 by ÜEsstaung of tert. Bv.-kjluwln made with oxide wex'don. Beiesplele fite '.0 $ J.uoQ $ ®n8. $ G _s äie fife the UiBsetaung rox'irendi't wzCmi hiSui \ e'ii, nlnü ^ iigiaciticslie Mieooysnafcoj like ÄtfeyleMii.eoeyu2i - ;; f ^: £ ™ ± mo ~ y? ^ -% rMl ± oQQgszmt, Τθύ, τβ, - methylondi-isocyanet »Pontsasotiiy ^ uiiiii-sooyuaicvfe imß. Iszaisethylondiisocyanat as well as other higher class of this homolossQH series "Branched-chain aliphatic! Diisocyanates, much like 3-ketyl-hexane-1,6-diisocyanate and 3-13 * -bicathylpentane-1,5-diisocyanate can be used. Suitable cyclicliphatic diisocyanates are cyclohexylene-1, 3 ~ im ~ 1 _? 4 ~ aiigocyanate or Kethylendicyoloheacyl-4 _? .4 ^l -'diisocyaiiat ₀ 2u dsn usable araliphatic Diisooyanatsn belong si- vr & p-Zylylenendiisooyanat as well as α, α, α ¹ »« '

909885/1607

original

The polyurethane seeds of the invention have logarithmic viscosity numbers in the range from 0.07 to 0.6, they are suitable for the production of SOrmlbodies, especially as compared with polymers of higher logarithmic viscosity, e.g. with polyurethanes, polyesters and polyamides of fiber-forming molecular weight, in order to stabilize this au, 2 ^{1 For} the latter purpose, the polyurethanes according to the invention preferably have a logarithmic viscosity number of 0.13 to 0.20. The logarithmic viscosity number is controlled in a known manner by using the correct ratio of the monomers and / or by using monofunctional chain termination agents.

The logarithmic yisoosity number is given by the size

defined, ¹ where ^ ₃ , the yisoosity of a dilute solution of the polymer, divided duroh the viscosity of the solvent in the same units xmd at the same temperature, means, while c means the concentration of the polymer in grams / 100 ml of solution. The logarithmic viscosity numbers of the polyurethanes according to the invention are determined at 25 ° C in Ν, Ν-dimethylacetamide at a concentration of 1 g / 100 ml of solution «

As indicated above, the primary use of the polyurethanes of the invention is their addition to long chain synthetic elastomeric segnented polyurethanes by physically blending them to stabilize them. These blessed polyurethanes v & t & wo. is generally made from prepolymers with terminal hydroxyl groups, such as polyesters or polyethers of low molecular weight, ie from about 600 to 3000, with terminal hydroxyl groups. By converting the prepolymerization with a small surplus of diatomaceous acid, a polymer intermediate product with end-end iboxanate groups is obtained, which then increases the chain length with a bifunctional, reactive hydrogen -

BATH ORIGINAL

atone-containing compound, such as with water, hydrazine, organic Diamines, oleols, dihydrazides, amino alcohols, etc., is subjected. These segmented polyurethanes are t> ® ~ and e.g. in the USA patents 2 929 801, 2 929 802,

2 929 803, 2 929 804, 2 953 839 ₉ 2 957 852, 2 999 839,

3,040,003 and 3,071,557.

The main use of this segmentedSH. Polyurethane is the production of spandex fibers for various kinds of clothing. If these clothes are washed in the usual chlorine-containing washing liquid, the pH of the washing liquid can vary considerably from about θ to 9.5, depending on the other fibers still present Schwante »® cotton fibers can reduce the pH value of the washing liquid SoB« by about 8.1. It has recently been found that the & i @ effect of a given amine as a stabilizer depends on that of the washing liquid. At pH Vfh & v about 11, for example, the polyaetfeaory specified in the ÜSA patent 2 999 839 bilieiernitt @ l accelerates
ester di @ discoloration and the breakdown of Spsmdszfasesa but at pH-W © rt®a in the aoraal white row from 8 to; 9,5 · B likewise tend to
hindered methacrylic acid ester geaäee
Document 1 104 127 on this »to accelerate the discoloration, among other things, to lower pH values within the nonaalei? Ifela © pH ranges tertiary amines is that they have only one effect on the physical characteristics at all pH values in the range from 3 to

Among other things, the advantages of the invention apart from the fact that the H-tert.-butyl group-containing PolfnrstSsssg -They are more flexible polyurethane foam beigeMe @ M w ± Tä ₉

9O9085 / 1SO7 "bad original

chen to nindeetene about 10 milliequivalents of the tert-butyl group bonded tertiary amino nitrogen $ e kg segmented polyurethanes, ie, "at least about 0.014 percent by weight, but to make available. The amount of this nitrogen should preferably be at least 0.05 percent by weight. With amounts of more than about 0.6 percent by weight, nan achieves no further advantages.

In the following examples, parts and percentages refer to Unless otherwise specified, on weighted quantities.

In the examples, the discoloration test under the action of a smoke and lever atmosphere is geoäss "Bu Pont Technical Information Bulletin L-33" of the Textile Fibers Department Technical Service Section of SI du Pont de Nemours and Company, Inc., Wilmington, Delaware, V .St.A., As well as according to the TJSA-Patentsohrifo 5 395 114 and the British patent specification 1 059 605.

The in the examples ajiö 'V' - * / ^ ¹ * - "^ © icMst © Selbgrad is also determined according to the USA- £ aten '@ s £ &? I £ ij 5 395 114 or the British patent specification 1 059 605" «

In the case of fibers, the test for degradation by chlorine is carried out by attaching the fibers to a rectangular hollow frame made of polyalkylene terephthalate, boiling the samples for 1 hour and then immersing them in an aqueous solution at 70 ° C for 50 minutes, which by mixing τ «η 5 , 0 ml of a hypochlorite bleaching agent ("Clorox ^M ) s 500 ml ¥ aas @ r, 1.0 g of an anionic detergent (" Tide ") and so much 0.1» norsel hydrochloric acid is produced that the pH is at 25 ° C. The tension ("force") of the fiber samples at break is determined before and after the action of the chlorine-containing bleaching agent then

- 7 -
909885/1607

Boiled for 60 minutes. Then the slides are 20 minutes the Exposed to the above-described chlorine-containing solution, Rinsed with cold water and dried at 70 ° 0 for 20 minutes. Before and after exposure to chlorine-containing bleach are the tension ("force") of the film samples 4-OO percent elongation and the elongation at break determined.

In the following examples all have the si- teri «butyl group Polyurethanes containing logarithm! See viscosity numbers (determined as above bass / irieber.) rwi & chen 0.07 and 0.6 on.

At Bpi β 1 1

100 g of a polyether prepared according to Example 1 of the ÜSA Patent Register 3 149 998 with terminal isocyanate groups and containing 3.27 i> H00 groups are dissolved in 200 g of Jff, l-diinethylacetamide and with 103 g of a solution of 0.51 g diethylamine and 8.4 g of a mixture of 60 Molprosont ithyXenäiaiBisa. and 20 mole percent 1,3-Cyoloh <y3Eylendiaain in 300 g H ,, H-Biai © tliyl.-aoetamid of the Eettenverlängsruiig subjected. This gust is mixed with a solution of a nicit-segmented polyurethane, which is prepared by adding (1) 0.05 ml of dibutylsine diacetate at room temperature to a mixture of 140 g of 4-t & rt _e 2utyl-4-azaheptanediol-2,6, 175 Stir in g of methylindioyclohesyl-4,4 ⁹ diisocyanate and 210 g of potassium dimethylacetamide and (2) keep the mixture at 70 ° C. for 90 minutes. The nicüt-aegiientiert © polyurethane is in such Meagß augeaetist _f that 5Q * 3 KLlIlaquivalente tertiary Aiainos-iokstoff to 1 kg segaentiertsn polyurethane "omitted. The PolyaerieatlOesug is poured ia with the help of a 0.178 aa-cylinder on Polyäthyleneterepathßlatplatten, so that after 12 si? Feige drying at 50 ° 0 Feliea with a diameter of 0.02794 * 0.00762 mm obtained. The results of degradation by chlorine are as follows:

«8 909885 / 1S07

BAO ORIGINAL

In friocfc ^ Ä2 ^ 3F-Gellifea iäustax & üe. 154 pounds

ηα, οϊι äei ⁵ I ^.: or 'al olea «85 g

Ex's tv $ 55 "

B α i ~ _ ^ ie 1 .. δ

A KismBg ^ ii-es jiig ^ euiiiJ ^^ tii ^ oX ^ 'a ^ eiC-g ^:. ·: 1 & H _? ^? i ™ -Di2is1; hyl · - ace ^ R ^ ta Wi ^ iI naoh example ;; -1- & ! »Ri-feie ^ bsa .ϊϊ: .- ί; ω. · Ι1? 3ο & 3Λ:? - ο

pheayläiiaoc ^ aiiab \ w & X'bhyieiiltinnii-T made with c3ü Aowoi-iii-mgaa, äß3s (1) the Polytkvtra-r.yS-liylenäthci'glj'kol o? .a Ttolekulargewich'u of 1Q00 has ₉ (2) avr - Mo.iJV & vuül% aiB ron ρ.ρ · »H.3thylcu.idiphenyldiisoöyKasst au Polytetraaif 'slij ^ Isnätiiorglyicol 1.60» C 3) the MolY ^ iiiältiiis of EthyleiLc-iaiEin au rer ~ capped glycol 0.980, ( Ifo3.7e? L \ altenni8 7oa flfe au Biä-fefcylömin 4 _f 95 _f (5) öcß ¹ "Feeiis-fcoregshci?. * 54 5S (6) die Li5ijm'gBvisöoai"öfö->;"3-> l Pf'i;. ^ Killing- ^ r, - !; · .Iu iv ^ s

"Yclofe (iir _J Eyl» 4 _f <l. ^I «.ird ^ '3O-3" / >>' nat and ü'-n iu ^ eoelie. ". Toggle

Λ.2, .1 © .. .1

■ "■ '■■■ * ■■' ji;" * - \ j '^ j

90988? - C7

& he Jcei-ae »'iioirJ

Man

¹⁰

f » Sis

so ar ..? \ Vbö?; B äiz ^ cli SSii

sample

A B C D

fria? li

ah aem

2.5 2.6

2.5 2.5 2.6

5.2 7.0 6.8

8.9 12.5

AJl

2 ,? 4.4-4.3 6.4 S ₉ I.

Dismantling by

sample

3 C

* rnokt

137

146 150

138

SOD

605 585

mo

to the

BruGhdeh'- force, - Irmcis.-

SS

160

in

I 6 (1?

(2) the molar ratio of p _} p ^f -HethylEdiphenyldiiOoyanat au poXytetramethylene ether glycol 1.70, (3) the MoX ratio dee as chain extender completed diamines from the blocked glycol 0.993 and (4} the hol ratio as chain extender used diamines to diethylamine 6.66 dea . Animal separate samples of the above solution of the segmented polyurethane are mixed with non-segmented Po?, Yt? J? 3thanes, which have been prepared by potting the misooyanates given in Table II with the sn fflycols given in the same table,

3L.a._b_A-lJL_g. il

MoX relation sample lilykoj Di? eoeyaa & t I ⁱ isocyanate: G3.ykol

A 3 "tert" butyl '3-Heacaine ethyl a-0.888

assapontaldiol-1 _? 5 diiso ij ap-it-

B 4 tert.ButyX-4 'HexEimethyleK - 0.901

a ^ aheptanediol-2,6 ßiieo ^ yanat

C 3 "tprt: .Buty:» - 3- MetliyXendi.ayclo- 0.86G

a ^ apfciitandiol-1, ^l ) hexyi-Hf ^ -'- di-

. ". aoeyanat

D 4-tert-butyl "" - K ^ fhy ^ en & ievolo- O ₅ 903

azaheptanediol-g, 6 heacyl-4 _; 4 '»di« = -

isoayenate

Each Gemioöh contains 35 »7 ^: " 0.5 MiXli! Iq.uiva'i.en'iia tertiary amino nitrogen ^ e kg segaentiorten Po ^ -jrethars * Jade lor solutions is irät li.tandioxid «IJlfcj.'eJOParinbir.upigijent \ ü .d a Harsartigon condensation product from p-iireool and DMnj with a molecular weight of about 2300. The Jn mixture contains 5 * C- #> fitandioac-.n- 0.0125 £ mteamariibla-i and 1.296 condensation product from p-Krepoi and Mvinyj benzol, be-eogen to the segiaentiert-i polyurethane. Iv.b jst-.er? .c ?? Ii'i.r ^ ngen are in lirirkHisstli-ciier Weiae nux '^ ii irorrkenspi ^ iisn ^ ase ^ n manufactured before 40 den. Di © lassrs '.uraeii. as above, described _f examined on AljbP.u üirrcb chlorine, I':. e tension ( ^Μ Η>? αίΐ ^Η ) "at break becomes ^ or xvlC after the JkTm. ^ h. TDc; t: n; Tnt _e I'is results are the iOLgender .;

- 11 ~

909065/1607

BATH ORIGINAL

? red: s

S. * ^ 19.18066 25th 5? -23 56 21 45 61 25th 54 39

1300 g Polytetr &isethyl'mälmerglylcoj. Kit with a v / ichtwahleBfflittel from 2050 turn at EäxiTu-äemper & tur u & tes? dry nitrogen with 334 g Metliyleadicyoloiieiiyl ^ i ^^ di isocyenat added ο Bas Gercisoh wirö i'iitor Eölirea to 53 ö erfcitst and hit 1 drop Diftiitylsismdila-amt varsstst ge des ^ iißataee des Dioatylsiir ^ diieTiratR © rises € ie '! atia raeoli to 11 ° C, when msii das Heat1; iOB8ßG? rigak dti ^ oii Brliiti? ®a 45 Mimten ar \ f 75 bie 30 ° Ö TaSIt ₉ eiitst-iat sia

holds. 800 g of this Voipo / .yii: vr: .3a * ^; ; p ait ^ HuPtMndige gritppon will be in 224? g lis'i-iiisso'luiflaectanid gslö ^ t, iie E © t teK-lengthened ariit 29 ⁷ rü oiaer 1 ₉ 0κ · ίθ1α 1 j 3'CycloliesylejidiaKin in K-Li- ^ iiaeuhylaoG-viEia imcl the! © t abrucä. ümn Kit 15? 0 i; ij ci: iei ^! 2 _f 0 «> r? Olai? Ei :. Lijeiinfe tob öyolo "

in Uyu-Mwotliy ^ o ^ tiruiicil i «.i? cbgeföiir» t · lin feil. these? dee ß ^ igmented PoX ^ L- ^ stfetms vrird ia.it © ime-r Jjösim ;. Sas Jn Seispiel ^ bargain £ »lieBclirisbeneri: iloht SoIy- Tersetzto The so-ei ha ^ ^ tene IiÖs sg enthüll;!?"& Eg se7.ti © RTE "? 35 lß.Xli-

tertiary Aninoetioketoff $ v kg aerated polyurethanes. In addition to the 3jösi22ig des aegaentierte Solyui'iaiie also titanium dioxide, 2- (2 »~ Hjdro: <: y-3 '-te ^ t _e toatyi-5

hydroxyphenyl} "propior4 ^r loz3rB] utliyl7 ^ ath2ii setj in equal amounts that the KonEcntratio & en an dsa vss-schiedsaeD 'U 7 ^, Oj 5 ^" bssiV. 1.Ü4- ^, bcsogeD. on clae segsentier-te. Polyurethane amount. Dvx-ch. ircskene-pi-nnen in Wa? .lchxss -Hfelfte ws:

9093 95/1607

BATH

fibers of 70 don made. The magicians will be, above wrote, subject to dismantling by üf'ilor. Me tension In the event of a break, υογ -and naoL dsa Tersuch with the Results determined:

Force t & / & on

ψ «ι ι n '*

freshly made n & cii dsm? c; rsucla

O _s 52 O _S 25 67

The practical upper ffrenae represents the amount of the IJ ~ _e tert-butyl group-containing polyurethanes geinäss animal invention, the polyurethanes segmentierton augeeetst v / Srdan eioll is about 15 Crewichteproze ^ t. Wi © "already mentioned, to the amount sufficient to at least 10 MillAäctuivalenta I-tert.Butylstiokstoff segmented per kg polyurethane Eiir provide au therefore intended to mix ai,. ·% N foria of li" $ © rt "butyl vorliagendo Msnge to Stio & atoff siinäesbonfä? 0 MilliäqtuiYalente per kg the E-tert-butyl groups contain polyurethane, that is, about 0.1 S-ewiohta percent, bet

BADOfiKSJMAL

Claims (1)

9th Apse 19Ö9 Β · Ι * you Btmt 4e Η 1. Bolyuretlisa, daeUirofe gelseanzeiclmet «äass © si» of the ipoly aerisatkette terti & fö AninostiekstoffatoisQ estisältj von. to which each at 2sw®i Eolilaiistoffateiie »öle-weäö-r au aooli to eiasm aroaatisehea Hing is" a ia Mmsthylacai-auiifl b © i 25 ° G in eiaes? Son «= from 1 g / 100 yes! Sösaag 7iscoeitätssahl i © Ber © iö1i iroa © twa O ₅ O? Ms 0.6 d © 3? allgeaeiasa for 0. 0 contains, m der E wsä B ¹ swsiwe ^ tig® sliplmtieeli © *, ψ aliplaatisehe o & sr eia tertiary 2. Bast H- ¹ # 1 © tertiSr® ^ äaostiolce East E ^f Ma feeaisasgtsis-isiisg ■. 903805 / iiÖfV - ■. ■ BATHROOM has, in which Alls has a lower AlfeyXenresät and t-Bw the 4. Polyurethane according to claim 1 Ms 3> gekennseichnet that H a jswei-valent cycloaliphatiöahisn H <sst _f in particular the ^ »^ ' 5. Polyurethane according to Mspjcuch 1 to 3 »öaduroh gakönnseichnet, that B tears the hexaraethylene 6. Polyurethane according to claim 1 to 5 »thereby gekennaeichnet, that there is a logarithinic ViBCOBity number in the range of 0.13 Ms 0.20. c Long-chain synthetic elaetomsree segmented polyurethane, characterized) that qb against the coloration under the effect of light, breath and leverage by physical inclusion of a steady amount of a polyurethane according to Änapruch 1 to & £ 5tai3ilized » 8. Molded body, characterized in that it consists of a naesh Claims stabilized segmented polyurethane "consists of * 9 «Easer, characterized by the fact that they are made from a® close claim ? stabilized, graded polyurethane » . - 15 - 909885/160; BATH ORIGINAL